Method Of Supercritical Fluid Fractionation Of Oil Seed Extraction Materials

ABSTRACT

Generally, a method of pressure regulated supercritical fluid fractionation of oil seed extraction materials which can be utilized to refine oil seed extraction material established in an amount of supercritical fluid. Specifically, a method of pressure regulated supercritical fluid fractionation of corn germ extraction material to produce a refined corn oil extraction material.

This United States Patent application is a continuation of U.S. patentapplication Ser. No. 13/428,612, filed Mar. 23, 2012, which is acontinuation of U.S. patent application Ser. No. 12/217,497, filed Jul.5, 2008, now U.S. Pat. No. 8,142,830, issued Mar. 27, 2012, which claimsthe benefit of U.S. Provisional Patent Application No. 60/958,472, filedJul. 6, 2007, each hereby incorporated by reference herein.

I. BACKGROUND

Generally, a method of pressure regulated supercritical fluidfractionation of oil seed extraction materials which can be utilized torefine oil seed extraction material established in an amount ofsupercritical fluid. Specifically, a method of pressure regulatedsupercritical fluid fractionation of corn germ extraction material toproduce a refined corn oil extraction material.

Oil Seed extraction materials which include materials extracted from theentirety or parts of various seeds such as corn (typically the corngerm), cotton, rape, safflower, sunflower, flax, or the like, can begenerated by a wide variety of extraction methods, such as, solventextraction, hydraulic pressing, expeller pressing, or the like. Usefulsolvents for solvent extraction can include hexane, n-hexane, isopropylalcohol, supercritical fluids, supercritical carbon dioxide, and othersimilar solvents.

There is a large commercial market for oil seed extraction materialssuitably refined to meet the varying standards for direct use as fuels,the production of fuels, the processing of foods, addition to foods, andfood. The oil seed extraction materials obtained by these extractionmethods exhibit a correspondingly wide range of compositions as mixturesof neutral extraction oils, fatty acids, and a greater or lesser amountof undesired impurities. For example, the undesired impurities in thecorn germ extraction material can include one or more of: free fattyacids (FFA) from the degradation of corn germ oil by hydrolysis,phosphatides (hydratable and non-hydratable), organic compounds whichcontribute certain colors, flavors or odors, particulates entrained bythe extracted corn germ extraction material, or the like.

A significant problem with the refining of oil seed extraction materialincluding corn germ extraction material may be that while a wide varietyof methods for the extraction of oil seed extraction material from oilseeds have developed over the past decades, relatively few methods ofrefining oil seed extraction material have developed over the sameperiod. For example, corn germ extraction material continues to berefined by addition of a base such as sodium hydroxide, soda ash, sodiumbicarbonate, potassium hydroxide, or the like, which reacts with FFA toproduce an emulsion of neutral corn germ extraction oils, a soap mass(often referred to as the “soap stock”), and residual base. The emulsioncan centrifuged to separate the neutral corn germ oils from the soapstock and the residual base. The neutral corn germ oils are typicallycombined with an amount of silica to trap residue soap stock, residualphosphorus, and trace metals. The silica being removed from the neutralcorn germ extraction oils by filtration. The resulting neutral corn germoils may be bleached to reduce color. The corn oil generated may besuitable for a wide variety of uses depending on the exact manner ofapplying the above-described general steps of the corn germ extractionmaterial refining process.

While this centrifugal refining process is typically suitable forprocessing oil seed extraction materials and specifically suitableacross the wide range of corn germ extraction material compositionsgenerated by the various corn germ extraction material extractiontechniques, it has certain disadvantages in that the centrifugalrefining process involves the utilization of equipment costly topurchase and maintain, the various extraction processes and thecentrifugal refining process may operate separate from one anotherwithout significant feed back from the refining process to theextraction process, and without limiting the disadvantages of thecentrifugal refining process, may be more costly per unit of refinedcorn germ extraction material than necessary based upon the higherquality of corn germ extract materials being generated by more recentlydeveloped corn germ extraction material extraction processes.

Interestingly, due to the prevalence and overall suitability ofconventional centrifugal refining process, developments in the refiningof oil seed extraction materials and specifically corn germ extractionmaterials may not have addressed refining of oil seed extractionmaterials or corn germ extract materials in bulk by any alternatenon-centrifugal extraction material refining process, but rather focuson the production of oil seed extraction material or corn germextraction material fractions enriched in certain compounds. Forexample, U.S. Pat. No. 5,932,261 describes a process for production of acarotene rich refined oil fraction from a corn germ extraction material.

To address the unresolved problems associated with the utilization ofconventional oil seed and corn germ extraction equipment and methods ofrefining oil seed extraction materials and specifically corn germextraction materials, the instant invention provides devices and methodsfor the pressure regulated supercritical fluid fractionation of oil seedextraction materials and specifically of corn germ extraction materials.

II. SUMMARY OF THE INVENTION

Accordingly, a broad object of embodiments of the invention can be toprovide a oil seed material production system which utilizes an amountof a supercritical fluid to remove an amount of oil seed extractionmaterial from ground whole or ground parts of oil seeds and subsequentlyfractionates the amount of oil seed extraction materials established inthe amount of supercritical fluid (also referred herein as the effluent)by passage through a series of oil seed extraction material separationzones each having an adjustable pressure within a fixed temperaturerange each producing a corresponding oil seed extraction materialfraction separable from the effluent in each oil seed extractionmaterial separation zone.

A second broad object of embodiments of the invention can be to providean oil seed extraction material separator which generates at least oneoil seed extraction material fraction suitable for the production ofbiodiesel or utilization as food grade oil without utilization ofconventional productions steps involving generation of soap stock andcentrifugation.

A third broad object of embodiments of the invention can be to provide aoil seed extraction material separator which provides three oil seedextraction material separation zones: a first providing an adjustablepressure within a fixed temperature range to generate a phosphatidefraction from an amount of effluent, a second providing an adjustablepressure within a fixed temperature range to generate a triglyceridefraction from an amount of effluent having the phosphatide fractionseparated in the first extraction material separation zone, and a thirdproviding an adjustable pressure within a fixed temperature range togenerate an FFA fraction from the effluent having the phosphatidefraction separated in the first extraction material separation zone andhaving the triglyceride fraction separated in the second extractionmaterial separation zone.

A fourth broad object of the invention can be to provide a corn germextraction material separator which provides three corn germ extractionmaterial separation zones: a first providing an adjustable pressurewithin a fixed temperature range to generate a phosphatide fraction froman amount of effluent, a second providing an adjustable pressure withina fixed temperature range to generate a triglyceride fraction from anamount of effluent having the phosphatide fraction separated in thefirst extraction material separation zone, and a third providing anadjustable pressure within a fixed temperature range to generate an FFAfraction from the effluent having the phosphatide fraction separated inthe first extraction material separation zone and having thetriglyceride fraction separated in the second extraction materialseparation zone.

Naturally, further objects of the invention are disclosed throughoutother areas of the specification, drawings, photographs, and claims.

III. A BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 provides a flow diagram of a particular embodiment of an oil seedextraction and oil seed extraction material fractionation system.

FIG. 2 provides an enlarged portion of the flow diagram shown in FIG. 1further providing a cut away of a part of an extraction vessel showingthe oil seed extraction zone containing an amount of oil seed material.

FIG. 3 provides an enlarged portion of the flow diagram shown in FIG. 1further providing cut away views of the separator vessels included inthe oil seed extraction material separator.

FIG. 4 provides a graph which plots density of supercritical carbondioxide against temperature for each of a plurality of supercriticalcarbon dioxide pressures and provides for each of a first separatorvessel (S-1), a second separator vessel (S-2), and a third separatorvessel (S-3) a corresponding window which bounds the separationparameters in which one of a phosphatide fraction, a triglyceridefraction, or a fatty acid fraction can be separated from an amount ofsupercritical carbon dioxide in which an amount of corn germ extractionmaterial is established.

IV. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Generally, a method of pressure regulated supercritical fluidfractionation of oil seed extraction materials which can be utilized torefine oil seed extraction material established in an amount ofsupercritical fluid. Specifically, a method of pressure regulatedsupercritical fluid fractionation of corn germ extraction material toproduce a refined corn oil extraction material.

First referring primarily to FIGS. 1 and 2, a non-limiting example of anoil seed extraction material production system (1) is shown. For thepurposes of this invention the term “oil seed” or “oil seeds” means theseed of corn, cotton, flax, sunflower, canola, sesame, linseed, soybean,peanuts, copra, safflower, mustard, brassica, rapeseed, or the like,whether in whole or comminuted to provide sufficiently small pieces ofseed or sufficiently small pieces of a part of the seed compatible witha method of oil extraction and specifically includes as non-limitingexample corn germ isolated from whole corn seed. The term “oil seedextraction material” for the purposes of this invention means thematerials extracted from the entirety or parts of the various oil seedsby any device or method of removal or extraction, such as, solventextraction, hydraulic pressing, expeller pressing, including thecorrespondingly wide range of compositions of neutral extraction oils,fatty acids, and a greater or lesser amount of undesired impurities. Theundesired impurities in the oil seed extraction material can include oneor more of: free fatty acids (FFA) from the degradation of corn germ oilby hydrolysis, phosphatids (hydratable and non-hydratable), organiccompounds which contribute certain colors, flavors or odors,particulates entrained by the extracted corn germ extraction material,or the like.

A non-limiting example of an oil seed extraction material productionsystem (1) which can be used to produce an amount of corn germextraction material (11)(see FIG. 2) can include a corn germ extractor(2)(for example, the cascade extractor shown in FIG. 1 which providesone or a plurality of corn germ extractor vessels (3) each of whichdefines a corn germ extraction zone (4)(see FIG. 2) inside of which anamount of corn germ (5) comminuted to provide a plurality of corn germparticles (6) can be located for fluidic engagement with an amount ofsupercritical carbon dioxide (7) to perform a corn germ extraction eventto produce an amount corn germ extraction material (11). Each of thecorn germ extractor vessels (3) can independently perform an extractionevent on an amount of corn germ (5) in manner which allows at least oneextractor vessel (3A)(shown in broken lines) to come off line for aperiod of time after the extraction event sufficient for removal of anamount of extracted corn germ (8) and introduce an amount of corn germ(5) for a subsequent extraction event.

While the embodiment of the corn germ extraction material productionsystem (1) shown in FIG. 1 utilizes a cascade extractor with an amountof supercritical carbon dioxide (7) as the extractant, as more fullydescribed in U.S. patent application Ser. No. 11/716,838, herebyincorporated by reference in the entirety herein, this is not intendedto limit the manner in which an amount of corn germ extract material(11) can be obtained from an amount of corn germ (5) or the manner inwhich an amount of oil seed extract material can be obtain from anamount of oil seed. Rather, it is intended that the description of thecorn germ extractor (2) be illustrative with respect to the numerous andvaried oil seed extractors and oil seed extraction processes which canbe utilized to obtain oil seed extraction material(s) including corngerm extraction materials (11) having the correspondingly wide range ofcompositions as above-described which can be received by the oil seedextraction material separator (14)(also referred to in the context ofthe non-limiting example which follows as a corn germ extractionmaterial separator) and processed as further described below.

Again referring primarily to FIGS. 1 and 2, each of the plurality ofcorn germ extractor vessels (3) can be coupled to a heat source (9)which generates an amount of heat sufficient to maintain the amount ofsupercritical carbon dioxide (7) at a temperature of between about 70°C. and about 120° C. during fluidic engagement with the amount of corngerm (5) located inside said corn germ extraction zone (4). The heatsource (9) can be coupled to a temperature adjustment element (10) whichcan monitor temperature of the amount of supercritical carbon dioxide(7) in the corn germ extraction zone (4) or can monitor other conditionsoutside of the corn germ extraction zone such as the amount of corn germextraction material (11) established (whether solubilized, carried, orentrained) in the amount of supercritical carbon dioxide (7) (the“effluent” (12)) which flows from the corn germ extraction zone (4), orother measure of the efficiency of the extraction event to allowcontinuous adjustment of the temperature of the amount of supercriticalcarbon dioxide (7) in the corn germ extraction zone (4) to maintain apreselected temperature, a preselected temperature profile, or apreselected corn germ extraction efficiency profile based on monitoringthe effluent (12) from the corn germ extraction zone (4). The corn germextractor (2) further includes a plurality of conduits and valves (13)configured to allow transfer of the amount of supercritical carbondioxide (7) into and away from the corn germ extraction zone (4).

Now referring primarily to FIG. 1, the oil seed extraction materialproduction system (1) can further include an oil seed extractionmaterial separator (14)(also referred to as a corn germ extractionmaterial separator in the context of examples of fractionating corn germextraction material (11)). As one non-limiting example in the context ofrefining an amount of corn germ extraction material (11), the oil seedextraction material separator (14) can include at least one separatorvessel (15) which defines at least one corn oil separation zone (16) inwhich the amount of corn germ extraction material (11) extracted fromthe amount of corn germ (5) and established in the amount ofsupercritical carbon dioxide (or other solvent depending on theextraction method utilized) can be separated from the amount ofsupercritical carbon dioxide (7)(or other solvent) by establishing oneor a plurality of corn germ extraction material separation conditions inthe at least one corn germ extraction material separation zone (16). Theat least one separator vessel (15) further includes a plurality ofseparator conduits and valves (17) configured to allow serial transferof the amount of effluent (12) into or between the at least one corn oilseparation zone (16) and transfer of a separated corn germ extractionmaterial fraction (18) and the separated amount of supercritical carbondioxide (7) away from the at least one corn oil separation zone (16).

Now referring primarily to FIG. 3, a non-limiting example of a corn germextraction material separator (14) includes a first separator vessel(19) the configuration of the internal surfaces defining within a firstcorn germ extraction material separation zone (20), a second separatorvessel (21) the configuration of the internal surfaces defining within asecond corn germ extraction material separation zone (22), and a thirdseparator vessel (23) the configuration of the internal surfacesdefining within a third corn germ extraction material separation zone(24).

Now referring primarily to FIGS. 1, 2, and 3, the effluent (12) exitingthe corn germ extractor (2) passes serially through each of the firstseparator vessel (19), the second separator vessel (21), and the thirdseparator vessel (23) each configured to establish conditions in therespective corn germ extraction material separation zones (20)(22)(24)which allow adjustable pressure of the effluent (12) of between about200 bar to about 400 bar, 150 bar and 300 bar, and about 75 bar to about100 bar respectively at temperatures respectively fixed at between about60° C. to about 110° C., about 60° C. to about 100° C. and about 40° C.to about 70° C.

Operation of a main pressure reduction generator (26) coupled to conduit(27), in part controls the pressure in the corn germ extraction materialseparation zones (20)(22)(24) at the same time the conduit valve (28)controls the flow of effluent (12) to the separator vessels(19)(21)(23). The auxiliary pressure reduction generators (29)(30)(31)downstream of each separator vessel (19)(22)(23) and heat exchangers(32)(33)(34) upstream of each separator vessel (19)(22)(23) operate tocontrol the conditions in each such separator vessel (19)(22)(23). Toobtain separated corn germ extraction material fractions (18) from theeffluent (12), the effluent (12) flows by operation of the main pressurereduction generator (26) in conduit (27) through a heat exchanger (32)in conduit (35) and into the first separator vessel (19).

For the purposes of describing the present invention, ranges may beexpressed as from “about” one particular value to “about” anotherparticular value. When such a range is expressed, another embodimentincludes from the one particular value to the other particular value.Similarly, when values are expressed as approximations, by use of theantecedent “about,” it will be understood that the particular valueforms another embodiment. It will be further understood that theendpoints of each of the ranges are significant both in relation to theother endpoint, and independently of the other endpoint. Moreover, forthe purposes of the present invention, the term “a” or “an” entityrefers to one or more of that entity. As such, the terms “a” or “an”,“one or more” and “at least one” can be used interchangeably herein.Furthermore, an element “selected from the group consisting of” refersto one or more of the elements in the list that follows, includingcombinations of two or more of the elements.

Now referring primarily to FIGS. 3 and 4, the effluent (12) entering thefirst corn germ extraction material separation zone (20) in the firstseparator vessel (19) can be maintained at a fixed temperature in therange of about 60° C. to about 110° C. and the pressure of the effluent(12) can be variably adjusted between about 200 bar and about 400 bar toachieve a density of the supercritical fluid (typically supercriticalcarbon dioxide) of between about 0.75 g/mL and about 0.85 g/mL toproduce a phosphatide fraction (36)(see conditions bounded by block S-1in FIG. 4). The phosphatide fraction (36) which separates out of theeffluent (12) in the first separator vessel (19) can accumulate as asolid material whether at the bottom of the first separator which can beperiodically removed or exits through the first separator vessel drainline (37) entrained in an amount of the effluent. This phosphatidefraction (36) comprises any one of or a mixture of various phosphorouscontaining lipids (or phospholipids) commonly referred to as lecithinwhich can serve as crystallization nuclei for condensation offlocculants in biodiesel.

Now referring primarily to FIG. 4 and Table 1, an increase in the totalamount of the phosphatide fraction (36) can be achieved by fixing thetemperature within a narrower temperature range of between about 70° C.and about 90° C. and adjusting pressure of the effluent (12) betweenabout 250 bar and about 350 bar to achieve a density of thesupercritical fluid of between about 0.75 g/mL and about 0.85 g/mL.Specifically in the non-limiting context of an amount of corn germextraction material established in an amount of supercritical carbondioxide, an even greater increase in total amount of the phosphatidefraction (36) can be achieved within a fixed range of temperature ofbetween about 60° C. and about 70° C. and adjusting pressure of theeffluent (12) between about 325 bar and about 350 bar to achieve adensity of the supercritical carbon dioxide of between about 0.75 g/mLand about 0.85 g/mL (total phospholipid increases with reduced densityto about 0.75 g/mL).

TABLE 1 1st Separator Data CO₂ Pressure Temp. Density TotalPhospholipids Experiment # MPa ° C. g/mL Wt. Percent Feedstock N/A N/A0.52 SM 70723 34.474 70 0.823 0.65 SM 70724 27.579 55 0.832 0.26 SM70725 34.474 60 0.860 0.52 SM 70731 41.369 65 0.881 0.12 SM 70780148.263 70 0.897 0.12 SM 707802 55.158 80 0.898 0.14 SM 707809 51.711 750.897 0.10 SM 707810 44.816 70 0.881 0.10 MPa = Megapascals 1 Megapascal= 10 bar

Again referring to Table 1 and in particular referring to FeedstockSM70725 as a non-limiting example, a crude corn oil feedstock can beobtained from ConAgra Foods Inc., Memphis, Tenn. having a phospholipidconcentration of 0.52 mg/g. 500 mL of the crude corn oil feedstock wasfed through a first separator by a high pressure diaphragm pump enablingcountercurrent contact between the crude corn oil feedstock andsupercritical carbon dioxide (also referred to as “supercritical CO₂”).The temperature in the separator was set at 60° C. in all the sections.The supercritical CO₂ supply pressure was maintained at about 34.474 MPaby a CO₂ pump. This temperature and pressure provided a pure supercritical carbon dioxide density of 0.960 mg/mL. The crude corn oilfeedstock was fed into the separator at an average rate of approximately2.6 mL/min; the supercritical carbon dioxide flow rate was kept at 3SLPM. Every ten minutes, readings were taken of the pressure inside thefirst separator, at the CO₂ pump and the high pressure diaphragm pump,also the temperatures at the top, center, and bottom of the separatorwere monitored. Finally the temperatures of supercritical CO₂ enteringand exiting the column were also recorded. The separator was operated inthe manner described above for 120 minutes. A bottom valve of theseparator was opened every ten minutes and a sample of liquid thatcondensed during the previous ten minute period was drawn from thecolumn. After reaching steady-state of pressures, temperatures and flowrates within the column, six samples from the bottom of the extractorwere combined and analyzed for phospholipid content. The phospholipidconcentration of the crude corn oil feed stock was unchanged byfractionation at these processing conditions and remained at 0.52 mg/gin the separator. Fractionation continued utilizing the same procedureat processing conditions representing both higher and lower pure carbondioxide densities as shown in Table 1. As can be seen from the table thephospholipid concentrations or amounts begin to selectively concentratein the first separator below a pure carbon dioxide density of about 825kg/m³.

Again referring primarily to FIGS. 3 and 4, the resulting effluent (12)proceeds from the first separator vessel (19) through the conduit (38),the auxiliary pressure reduction generator (29) and the heat exchanger(33) into the second separator vessel (21). The temperature of theeffluent (12) can be adjusted in the heat exchanger (33), and thepressure of the fluid in the second separator vessel (21) can beadjusted by the downstream pressure reduction generator (30).Fractionation conditions in the second corn germ extraction materialseparation zone (22) of the second separator vessel (21) can beestablished to provide a fixed temperature in the range of about 60° C.to about 100° C. and a pressure adjusted within range of about 150 barto about 300 bar to achieve a density of the supercritical fluid(typically supercritical carbon dioxide) of between about 0.62 g/mL andabout 0.75 g/mL to produce a triglyceride fraction (38)(see conditionsbounded by block S-2 in FIG. 4). The triglyceride fraction (38) whichseparates out of the effluent (12) in the second separator vessel (21)exits through the second separator vessel drain line (39). Thistriglyceride fraction (38) comprises glyceride in which the glycerol isesterified with three fatty acids. It is the main constituent of thecorn germ extraction material (11) established in the effluent (12).

Now referring primarily to FIG. 4 and Table 2, conditions can beestablished in the second corn germ extraction material separation zone(22) which allows the separation of the triglyceride fraction (36) whilethe free fatty acids remain soluble in the effluent (12). Specificallyin the non-limiting context of an amount of corn germ extractionmaterial having the phospholipid fraction removed the triglyceridefraction (36) can be separated while the FFAs remain soluble in theeffluent (12) by fixing the temperature within a temperature range ofbetween about 70° C. and about 90° C. and adjusting pressure of theeffluent (12) between about 175 bar and about 250 bar to achieve adensity of the supercritical fluid of between about 0.62 g/mL and about0.75 g/mL. Specifically in the non-limiting context of an amount of corngerm extraction material established in an amount of supercriticalcarbon dioxide, an even greater increase in free fatty acid in theeffluent transferred from the second corn germ extraction materialseparation zone (22) can be achieved within a fixed range of temperatureof between about 60° C. and about 65° C. and adjusting pressure of theeffluent (12) between about 195 bar and about 250 bar to achieve adensity of the supercritical carbon dioxide of between about 0.72 g/mLand about 0.76 g/mL. As to certain embodiments of the invention, even agreater amount of FFAs remain soluble in the effluent (12) at a fixedtemperature of about 60° C. and adjusting the pressure to about 0.72g/mL.

TABLE 2 2^(nd) Separator Data CO₂ Pressure Temp. Density Free Fatty Acidin Experiment # MPa ° C. g/mL Effluent mg/g Feedstock N/A N/A 1.74 SM70613-1 19.926 60 0.722 18.82 SM 70614-1 25.028 65 0.762 16.26 SM70615-1 20.684 55 0.764 10.99 SM 70618-1 19.995 45 0.813 9.63 SM 70618-223.994 75 0.698 11.70 SM 70619-1 17.995 45 0.789 11.58 MPa = Megapascals1 Megapascal = 10 bar

Again referring to Table 2, crude corn oil feedstock was obtained fromConAgra Foods Inc., Memphis, Tenn. with a free fatty acid concentrationof 1.74 mg/g. 500 ml of crude corn oil feedstock was fed through thesecond separator by a high pressure diaphragm pump to enable thecountercurrent contact between the feedstock and supercritical CO₂. Thetemperature in the separator column was set at 60° C. in all thesections. The supercritical CO₂ supply pressure was 19.926 MPa. Thistemperature and pressure represented a pure carbon dioxide density of0.722 g/mL. The feedstock was fed into the column at an average of rateof approximately 2.6 mL/min; the carbon dioxide flow rate was kept at 3SLPM. Every ten minutes, readings were taken of the pressure inside thecolumn, at the CO₂ pump and the diaphragm feedstock pump, also thetemperatures at the top, center, and bottom of the fractionation columnwere monitored. Finally the temperatures of the supercritical CO₂entering and exiting the column were also recorded. The second separatorwas operated in the manner described above for 120 minutes. Afterreaching steady-state of pressures, temperatures and flow rates withinthe column a sample was obtained of the effluent exiting the secondseparator under steady-state operating conditions and analyzed for FFAcomposition. The FFA concentration was folded by fractionation at theseprocessing conditions by a factor of about 10.82 from 1.74 mg/g to 18.82mg/g (see Table 2, SM 70613-1). Fractionation continued utilizing thesame procedure at processing conditions representing both higher andlower pure carbon dioxide densities as shown in Table 2. As can be seenfrom the table the FFA concentrations begin to selectively concentrateapproaching 19% in the third separator below a pure carbon dioxidedensity of about 725 kg/m³.

Now referring primarily to FIGS. 3 and 4, the resulting effluent (12)proceeds from the second separator vessel (21) through the conduit (40),the auxiliary pressure reduction generator (30) and the heat exchanger(34) into the third separator vessel (23). The temperature of theeffluent (12) can be adjusted in the heat exchanger (34), and thepressure of the fluid in the third separator vessel (23) can be adjustedby the downstream pressure reduction generator (31). Fractionationconditions in the third corn germ extraction material separation zone(24) of the third separator vessel (23) establish a fixed temperature inthe range of about 40° C. to about 70° C. and the pressure can beadjusted within the range of about 75 bar to about 100 bar to achieve adensity of the supercritical fluid (typically supercritical carbondioxide) of between about 0.1 g/mL and about 0.3 g/mL which allowsseparation of the FFA fraction (41) from the effluent (see conditionsbounded by block S-3 in FIG. 4). The FFA fraction (41) which separatesout of the effluent (12) in the third separator vessel (23) exitsthrough the third separator vessel drain line (42). This FFA fraction(41) comprises a carboxylic acid often with a long unbranched aliphatictail (chain), which is either saturated or unsaturated. Carboxylic acidsas short as butyric acid (4 carbon atoms) are considered to be fattyacids, while fatty acids derived from natural fats and oils may beassumed to have at least 8 carbon atoms, such as caprylic acid (octanoicacid). In regard to biodiesel production, if the free fatty acid levelis too high it may cause problems with soap formation and the separationof the glycerin by-product downstream. It is also known that high freefatty acids levels may not be good for human health.

Now referring primarily to FIG. 4, in increase in total amount of freefatty acids in the FFA fraction (41) can be achieved by fixing thetemperature within a narrower temperature range of between about 45° C.and about 65° C. and adjusting pressure of the effluent (12) betweenabout 85 bar and about 95 bar to achieve a density of the supercriticalfluid of between about 0.1 g/mL and about 0.3 g/mL. Specifically in thenon-limiting context of an amount of corn germ extraction materialestablished in an amount of supercritical carbon dioxide, an evengreater increase in total phospholipids in the phosphatide fraction (36)can be achieved within a fixed range of temperature of between about 50°C. and about 60° C. and adjusting pressure of the effluent (12) betweenabout 80 bar and about 90 bar to achieve a density of the supercriticalcarbon dioxide of between about 0.1 g/mL and about 0.3 g/mL.

It can be appreciated that the corn germ extraction material separator(14) shown in FIG. 3 may be operated with additional separator vesselsto re-fractionate any of separated corn germ extraction materialfractions (18) to further isolate additional extraction materialfractions, or may be operated with additional separator vessels inseries to isolate additional extraction material fractions, or may beoperated to by-pass the first separator vessel (19) or the secondseparator vessel (21) or both. Also, a two step fractionation of corngerm extraction material (11) entrained in the effluent (12) can becarried out between the first separator vessel (19) and the secondseparator vessel (21).

Use of the corn germ extraction material separator (14) as shown in FIG.3 and utilized as above-describe can yield a quality of food grade corngerm extraction material which exhibits the characteristics set out inTable I.

TABLE I ATTRIBUTE DESCRIPTOR MIN MAX UOM Free Fatty n/a 0.01 0.06 %Acids Free Fatty n/a 0.01 0.05 % Acids PV n/a 0.0 0.5 meq/kg PV n/a 0.01.0 meq/kg OSI @110 deg F. 6.5 n/a hours AOM n/a 15 n/a hours FlavorFresh tbd tbd Hedonic Lovibond Red Color n/a 3.0 n/a Moisture n/a n/a0.03 % Fatty Acid Palmitic Acid 9.0 15.0 % Composition Fatty AcidStearic Acid 1.0 4.0 % Composition Fatty Acid Oleic 24.0 29.0 %Composition Fatty Acid Linoleic Acid 55.0 63.0 % Composition Fatty AcidLinoleic Acid n/a <2 % Composition para- n/a n/a 6.0 avu AnisidinePhosphorous n/a n/a 5.0 ppm

Again referring to FIG. 1, the resulting amount of carbon dioxide (43)proceeds from the third separator vessel (23) through the conduit (44)under the influence of the auxiliary pressure reduction generator (31)to the carbon dioxide recycle assembly (45)(see FIG. 1) which furtherinclude a condenser (46) which provides condensing conditions toestablish the amount of carbon dioxide (43) in a phase compatible with apressure generator (47) which establishes and maintains the amount ofsupercritical carbon dioxide (7) at pressures between about 7,000 psiand about 12,000 psi in the corn germ extraction zone (4). The pressuregenerator (47) can be coupled to a pressure adjustment element (48)which can monitor the pressure of the amount supercritical carbondioxide (7) in the corn germ extraction zone (4) or can monitor otherconditions outside of the corn germ extraction zone (4) such as theamount of corn oil solubilized in the effluent (12), or other measure ofthe efficiency of the extraction event to allow continuous adjustment ofthe pressure of the amount of supercritical carbon dioxide (7) in thecorn germ extraction zone (4) to establish or maintain a preselectedpressure, a preselected pressure profile, or a preselected corn germextraction efficiency profile based on monitoring the effluent (12) fromthe corn germ extraction zone (4).

Now again referring primarily to FIG. 1, it can be understood that ifthe flow rate of the supercritical carbon dioxide (7) in the corn germextraction zone (4) has a constant velocity (although in practice thevelocity can also be varied) then the effects of the alteration of thesupercritical carbon dioxide extraction conditions as to a temperatureand a pressure can be evaluated as to effect on a ratio of the amount ofsupercritical carbon dioxide (7) at a given temperature and pressure tothe amount of corn germ (16)(wt./wt.) (also referred to as the “solventto feed ratio”) to reach a particular extraction event end point such asan amount of corn germ extraction material (11) of about twenty percentof the amount of the corn germ (5) (wt./wt.). For example, if thesolvent to feed ratio is about 20 to 1 to obtain an amount of corn germextraction material (11) of twenty percent of the weight of the amountof the corn germ (16) extracted, then for each ton of corn germextraction material (11) extracted about twenty tons of supercriticalcarbon dioxide (7) would be utilized. If the solvent to feed ration isabout 2 to 1, then for each ton of an amount of corn germ extractionmaterial (11) extracted two tons of supercritical carbon dioxide (7)would be utilized and so forth. If the corn germ extraction materialproduction system (1) processes 300 tons of corn germ (5) per day at asolvent to feed ratio of about 20 to 1 then about 6,000 tons ofsupercritical carbon dioxide (7) would pass through the corn germextraction zone (4) of the corn germ extractor (2) and be recovered bythe carbon dioxide recycle assembly (45) per day. However, if the corngerm extraction material production system (1) processes the same 300tons of corn germ (5) per day at a solvent to feed ratio of about 2 to 1then only 600 tons of supercritical carbon dioxide (7) would passthrough the corn germ extraction zone (4) of the corn germ extractor (2)and be recovered by the carbon dioxide recycle assembly (45) per day.Accordingly, the corn germ extractor (2) can be configured to allow forprocessing of the corresponding amount of effluent (12). Even if theconfiguration of the corn germ extractor (2) remains substantially thesame regardless of the solvent to feed ratio because the mass of theamount of corn germ (5) extracted remains constant, it can be understoodthat at least the components of the a corn germ extraction materialseparator (14) and the carbon dioxide recycle assembly (45) would benecessarily scaled upward or downward as solvent to feed ratio increasesor decreases.

As can be easily understood from the foregoing, the basic concepts ofthe present invention may be embodied in a variety of ways. Theinvention involves numerous and varied embodiments of corn germextraction material production system and methods of making and usingsuch corn germ extraction material production system and making andusing corn germ extraction material. As such, the particular embodimentsor elements of the invention disclosed by the description or shown inthe figures accompanying this application are not intended to belimiting, but rather exemplary of the numerous and varied embodimentsgenerically encompassed by the invention or equivalents encompassed withrespect to any particular element thereof. In addition, the specificdescription of a single embodiment or element of the invention may notexplicitly describe all embodiments or elements possible; manyalternatives are implicitly disclosed by the description and figures.

It should be understood that each element of an apparatus or each stepof a method may be described by an apparatus term or method term. Suchterms can be substituted where desired to make explicit the implicitlybroad coverage to which this invention is entitled. As but one example,it should be understood that all steps of a method may be disclosed asan action, a means for taking that action, or as an element which causesthat action. Similarly, each element of an apparatus may be disclosed asthe physical element or the action which that physical elementfacilitates. As but one example, the disclosure of a “corn oilseparator” should be understood to encompass disclosure of the act of“separating corn oil” whether explicitly discussed or not and,conversely, were there effectively disclosure of the act of “separatingcorn oil”, such a disclosure should be understood to encompassdisclosure of a “corn oil separator” and even a “means for separatingcorn oil.” Such alternative terms for each element or step are to beunderstood to be explicitly included in the description.

In addition, as to each term used it should be understood that unlessits utilization in this application is inconsistent with suchinterpretation, common dictionary definitions should be understood to beincluded in the description for each term as contained in the RandomHouse Webster's Unabridged Dictionary, second edition, each definitionhereby incorporated by reference.

Thus, the applicant(s) should be understood to claim at least: i) eachof the corn germ extraction material production systems herein disclosedand described, ii) the related methods disclosed and described, iii)similar, equivalent, and even implicit variations of each of thesedevices and methods, iv) those alternative embodiments which accomplisheach of the functions shown, disclosed, or described, v) thosealternative designs and methods which accomplish each of the functionsshown as are implicit to accomplish that which is disclosed anddescribed, vi) each feature, component, and step shown as separate andindependent inventions, vii) the applications enhanced by the varioussystems or components disclosed, viii) the resulting products producedby such systems or components, ix) methods and apparatuses substantiallyas described hereinbefore and with reference to any of the accompanyingexamples, x) the various combinations and permutations of each of theprevious elements disclosed.

The background section of this patent application provides a statementof the field of endeavor to which the invention pertains. This sectionmay also incorporate or contain paraphrasing of certain United Statespatents, patent applications, publications, or subject matter of theclaimed invention useful in relating information, problems, or concernsabout the state of technology to which the invention is drawn toward. Itis not intended that any United States patent, patent application,publication, statement or other information cited or incorporated hereinbe interpreted, construed or deemed to be admitted as prior art withrespect to the invention.

The claims set forth in this specification, if any, are herebyincorporated by reference as part of this description of the invention,and the applicant expressly reserves the right to use all of or aportion of such incorporated content of such claims as additionaldescription to support any of or all of the claims or any element orcomponent thereof, and the applicant further expressly reserves theright to move any portion of or all of the incorporated content of suchclaims or any element or component thereof from the description into theclaims or vice-versa as necessary to define the matter for whichprotection is sought by this application or by any subsequentcontinuation, division, or continuation-in-part application thereof orto obtain any benefit of reduction in fees pursuant to, or to complywith the patent laws, rules, or regulations of any country or treaty,and such content incorporated by reference shall survive during theentire pendency of this application including any subsequentcontinuation, division, or continuation-in-part application thereof orany reissue or extension thereon.

The claims set forth below, if any, are intended describe the metes andbounds of a limited number of the preferred embodiments of the inventionand are not to be construed as the broadest embodiment of the inventionor a complete listing of embodiments of the invention that may beclaimed. The applicant does not waive any right to develop furtherclaims based upon the description set forth above as a part of anycontinuation, division, or continuation-in-part, or similar application.

1-19. (canceled)
 20. A method of fractionating oil seed extractionmaterial, comprising the steps of: a) establishing an amount of oil seedextraction material in an amount of supercritical carbon dioxide in afirst oil seed extraction material separation zone at a temperature ofbetween about 60° C. and about 110° C.; b) adjusting pressure of saidamount of oil seed extraction material in said amount of supercriticalcarbon dioxide in said first oil seed extraction material separationzone to between about 200 bar and about 400 bar to achieve a density ofsaid supercritical fluid of between about 0.75 g/mL and about 0.85 g/mL;and c) separating a phosphatide fraction from said oil seed extractionmaterial in said amount of supercritical carbon dioxide resulting in atriglyceride fraction and a fatty acid fraction remaining in said amountof supercritical carbon dioxide.
 21. The method of fractionating oilseed extraction material as described in claim 20, further comprisingthe steps of: a) delivering said amount of oil seed extraction materialin said amount of supercritical carbon dioxide having said phosphatidefraction separated in said first oil seed extraction material separationzone to a second oil seed extraction material separation zone; b)maintaining said amount of oil seed extraction material in said amountof supercritical carbon dioxide having said phosphatid fractionseparated in said first oil seed extraction material separation zone ata temperature of between about 60° C. and about 100° C.; c) adjustingpressure of said amount of oil seed extraction material in said amountof supercritical carbon dioxide having said phosphatid fractionseparated in said first oil seed extraction material separation zone tobetween about 150 bar and about 300 bar to achieve a density of saidsupercritical fluid of between about 0.65 g/mL and about 0.75 g/mL; andd) separating a triglyceride fraction from said oil seed extractionmaterial in said amount of supercritical carbon dioxide having saidphosphatide fraction separated in said first oil seed extractionmaterial separation zone.
 22. The method of fractionating oil seedextraction material as described in claim 21, further comprising thesteps of: a) delivering said amount of oil seed extraction material insaid amount of supercritical oil seed having said phosphatide fractionseparated in said first oil seed extraction material separation zone andsaid triglyceride fraction separated in said second oil seed extractionmaterial separation zone to a third oil seed extraction materialseparation zone; b) maintaining said amount of oil seed extractionmaterial in said amount of supercritical carbon dioxide having saidphosphatid fraction separated in said first oil seed extraction materialseparation zone and said triglyceride fraction separated in said secondoil seed extraction material separation zone at a temperature of betweenabout 40° C. and about 70° C.; c) adjusting pressure of said amount ofoil seed extraction material in said amount of supercritical carbondioxide having said phosphatid fraction separated in said first oil seedextraction material separation zone and said triglyceride fractionseparated in said second oil seed extraction material separation zone tobetween about 75 bar and about 100 bar to achieve a density of saidsupercritical fluid of between about 0.10 g/mL and about 0.30 g/mL; andd) separating an free fatty acid fraction from said oil seed extractionmaterial in said amount of supercritical carbon dioxide having saidphosphatid fraction separated in said first oil seed extraction materialseparation zone and said triglyceride fraction separated in said secondoil seed extraction material separation zone.
 23. The method offractionating oil seed extraction material as described in claim 22,wherein said step of maintaining said amount of oil seed extractionmaterial in said amount of supercritical carbon dioxide in said firstoil seed extraction material separation zone at a temperature of betweenabout 60° C. and about 110° C. comprises the step of maintaining saidamount of oil seed extraction material in said amount of supercriticalcarbon dioxide in said first oil seed extraction material separationzone at a temperature of between about 70° C. and about 90° C.
 24. Themethod of fractionating oil seed extraction material as described inclaim 23, wherein said step of adjusting pressure of said amount of oilseed extraction material in said amount of supercritical carbon dioxidein said first oil seed extraction material separation zone to betweenabout 200 bar and about 400 bar to achieve a density of saidsupercritical fluid of between about 0.75 g/mL and about 0.85 g/mLcomprises the step of adjusting pressure of said amount of oil seedextraction material in said amount of supercritical carbon dioxide insaid first oil seed extraction material separation zone to between about250 bar and about 350 bar to achieve a density of said supercriticalfluid of between about 0.75 g/mL and about 0.85 g/mL.
 25. The method offractionating oil seed extraction material as described in claim 24,wherein said step of maintaining said amount of oil seed extractionmaterial in said amount of supercritical carbon dioxide having saidphosphatid fraction separated in said first oil seed extraction materialseparation zone at a temperature of between about 60° C. and about 100°C. comprises the step of maintaining said amount of oil seed extractionmaterial in said amount of supercritical carbon dioxide having saidphosphatid fraction separated in said first oil seed extraction materialseparation zone at a temperature of between about 70° C. and about 90°C.
 26. The method of fractionating oil seed extraction material asdescribed in claim 25, wherein said step of adjusting pressure of saidamount of oil seed extraction material in said amount of supercriticalcarbon dioxide having said phosphatid fraction separated in said firstoil seed extraction material separation zone to between about 150 barand about 300 bar to achieve a density of said supercritical fluid ofbetween about 0.65 g/mL and about 0.75 g/mL comprises the step ofadjusting pressure of said amount of oil seed extraction material insaid amount of supercritical carbon dioxide having said phosphatidfraction separated in said first oil seed extraction material separationzone to between about 175 bar and about 250 bar to achieve a density ofsaid supercritical fluid of between about 0.65 g/mL and about 0.75 g/mL.27. The method of fractionating oil seed extraction material asdescribed in claim 26, wherein said step of maintaining said amount ofoil seed extraction material in said amount of supercritical carbondioxide having said phosphatid fraction separated in said first oil seedextraction material separation zone and said triglyceride fractionseparated in said second oil seed extraction material separation zone ata temperature of between about 40° C. and about 70° C. comprises thestep of maintaining said amount of oil seed extraction material in saidamount of supercritical carbon dioxide having said phosphatid fractionseparated in said first oil seed extraction material separation zone andsaid triglyceride fraction separated in said second oil seed extractionmaterial separation zone at a temperature of between about 45° C. andabout 65° C.
 28. The method of fractionating oil seed extractionmaterial as described in claim 27, wherein said step of adjustingpressure of said amount of oil seed extraction material in said amountof supercritical carbon dioxide having said phosphatid fractionseparated in said first oil seed extraction material separation zone andsaid triglyceride fraction separated in said second oil seed extractionmaterial separation zone to between about 75 bar and about 100 bar toachieve a density of said supercritical fluid of between about 0.10 g/mLand about 0.30 g/mL comprises the step of adjusting pressure of saidamount of oil seed extraction material in said amount of supercriticalcarbon dioxide having said phosphatid fraction separated in said firstoil seed extraction material separation zone and said triglyceridefraction separated in said second oil seed extraction materialseparation zone to between about 80 bar and about 95 bar to achieve adensity of said supercritical fluid of between about 0.10 g/mL and about0.30 g/mL.
 29. The method of fractionating oil seed extraction materialas described in claim 28, wherein said step of maintaining said amountof oil seed extraction material in said amount of supercritical carbondioxide in said first oil seed extraction material separation zone at atemperature of between about 70° C. and about 90° C. comprises the stepof maintaining said amount of oil seed extraction material in saidamount of supercritical carbon dioxide in said first oil seed extractionmaterial separation zone at a temperature of between about 75° C. andabout 85° C.
 30. The method of fractionating oil seed extractionmaterial as described in claim 29, wherein said step of adjustingpressure of said amount of oil seed extraction material in said amountof supercritical carbon dioxide in said first oil seed extractionmaterial separation zone to between about 250 bar and about 350 bar toachieve a density of said supercritical fluid of between about 0.75 g/mLand about 0.85 g/mL comprises the step of adjusting pressure of saidamount of oil seed extraction material in said amount of supercriticalcarbon dioxide in said first oil seed extraction material separationzone to between about 275 bar and about 325 bar to achieve a density ofsaid supercritical fluid of between about 0.75 g/mL and about 0.85 g/mL.31. The method of fractionating oil seed extraction material asdescribed in claim 30, wherein said step of maintaining said amount ofoil seed extraction material in said amount of supercritical carbondioxide having said phosphatid fraction separated in said first oil seedextraction material separation zone at a temperature of between about70° C. and about 90° C. comprises the step of maintaining said amount ofoil seed extraction material in said amount of supercritical carbondioxide having said phosphatid fraction separated in said first oil seedextraction material separation zone at a temperature of between about75° C. and about 85° C.
 32. The method of fractionating oil seedextraction material as described in claim 31, wherein said step ofadjusting pressure of said amount of oil seed extraction material insaid amount of supercritical carbon dioxide having said phosphatidfraction separated in said first oil seed extraction material separationzone to between about 175 bar and about 250 bar to achieve a density ofsaid supercritical fluid of between about 0.65 g/mL and about 0.75 g/mLcomprises the step of adjusting pressure of said amount of oil seedextraction material in said amount of supercritical carbon dioxidehaving said phosphatid fraction separated in said first oil seedextraction material separation zone to between about 195 bar and about230 bar to achieve a density of said supercritical fluid of betweenabout 0.65 g/mL and about 0.75 g/mL.
 33. The method of fractionating oilseed extraction material as described in claim 32, wherein said step ofmaintaining said amount of oil seed extraction material in said amountof supercritical carbon dioxide having said phosphatid fractionseparated in said first oil seed extraction material separation zone andsaid triglyceride fraction separated in said second oil seed extractionmaterial separation zone at a temperature of between about 45° C. andabout 65° C. comprises the step of maintaining said amount of oil seedextraction material in said amount of supercritical carbon dioxidehaving said phosphatid fraction separated in said first oil seedextraction material separation zone and said triglyceride fractionseparated in said second oil seed extraction material separation zone ata temperature of between about 50° C. and about 60° C.
 34. The method offractionating oil seed extraction material as described in claim 33,wherein said step of adjusting pressure of said amount of oil seedextraction material in said amount of supercritical carbon dioxidehaving said phosphatid fraction separated in said first oil seedextraction material separation zone and said triglyceride fractionseparated in said second oil seed extraction material separation zone tobetween about 80 bar and about 95 bar to achieve a density of saidsupercritical fluid of between about 0.10 g/mL and about 0.30 g/mLcomprises the step of adjusting pressure of said amount of oil seedextraction material in said amount of supercritical carbon dioxidehaving said phosphatid fraction separated in said first oil seedextraction material separation zone and said triglyceride fractionseparated in said second oil seed extraction material separation zone tobetween about 80 bar and about 90 bar to achieve a density of saidsupercritical fluid of between about 0.10 g/mL and about 0.30 g/mL. 35.The method of fractionating oil seed extraction material as described inclaim 34, wherein oil seed extraction material comprises corn germextraction material.